Trimerization of organic isocyanates

ABSTRACT

A process for trimerizing organic isocyanates by mixing said isocyanates with a complex of a basic alkali metal salt and a macrocyclic polyether.

United States Patent Inventor Appl. No.

Charles John Pedersen Salem, N-J.

Nov. 8, 1968 Nov. 23, 1971 E. I. du Pont de Nemouis and CompanyWilmington, Del.

Continuation-impart of application Ser. No. 588,302, Oct. 21, 1966, nowabandoned which is a continuation-in-part of application Ser. No.358,937, Apr. 10, 1964, now abandoned. This application Nov. 8, 1968,Ser. No. 774,493

TRLMERIZATION OF ORGANIC ISOCYANATES 16 Claims, No Drawings 52 U.S.Cl .L..260/248NS,

260/775 NC, 260/338, 260/345.9, 260/613 D [51 Int. Cl. C07d 55/38 [50]Field of Search 260/248 NS, 77.5, 77.5 NC

[56] References Cited UNITED STATES PATENTS 3,330,828 7/ 1967 Grogler etal 260/248 Priniary Examiner-John M. Ford Attorneys-Vemon R, RiceABSTRACT: A process for trimerizing organic isocyanates by mixing saidisocyanates with a complex of a basic alkali metal salt and amacrocyclic polyether.

TRIMERIZATION OF ORGANIC ISOCYANATES Related Applications Thisapplication is a continuation-in-part of copending Application Ser. No.588,302, filed Oct. 21,l966, which in turn is a continuation-in-part ofUS. Application Ser. No. 358,937, filed Apr. 10, 1964 both of whichapplications are now abandoned.

BACKGROUND OF THE INVENTION It is well-known that isocyanatecompositions of various types in combination with active hydrogencompounds are useful in the preparation of numerous types of importantcommercial products, such as polyurethane coatings, elastomers andfoams. ln order to introduce special effects into these products, it isoften necessary to modify the isocyanate composition used prior toreacting it with the active hydrogen compound, e.g., by preparingisocyanate-terminated prepolymers. Another important modification is thereaction of a portion of the isocyanato groups present to formisocyanate trimers (isocyanurates) in the isocyanate composition whichis then reacted with such compounds as polyols, polyamines and water toform useful products. Such partially trimerized isocyanate compositionshave reduced volatility and toxicity, increased light stability andbecause of their higher functionality, are especially valuable inpreparing tough, highly insoluble polyurethanes.

It is known that aliphatic and aromatic isocyanates form trimers whentreated with various basic catalysts. U.S. Pat. No. 2,978,449 to Franceand Lister discloses the use of basic catalysts such as sodium hydroxideand potassium acetate; US. Pat. No. 2,801,244 teaches the trimerizationof aromatic isocyanates by use of phosphine catalysts and British Pat.No. 1,001,746 discloses compounds containing ethylene imine rings ascatalysts for isocyanurate formation.

The prior art methods for trimerizing isocyanates have had certaindisadvantages, however. Some of the catalysts recommended are unsafe tohandle, some must be used in relatively high concentrations, and ingeneral the prior art catalysts tend to give isocyanate condensates of ahigher degree of polymerization than the simple trimers, which for manypurposes are preferred.

SUMMARY OF THE INVENTION According to this invention a process isprovided for trimerizing an organic isocyanate which comprisesessentially mixing said isocyanate with a complex of a basic alkalimetal salt and at least one mole per gram atom of the cation of saidcompound of a macrocyclic polyether consisting of at least one vicinalarylene dioxy group or derivative thereof joined to form a macrocyclicpolyether ring of at least 14 carbon atoms by a,w-diprimary alkylenegroups or cub-diprimary alkylene ether groups, the oxygen atoms of saidmacrocyclic ring being separated by two or three atoms.

DETAILED DESCRIPTION The macrocyclic polyethers described above willhereinafter be referred to as crown compounds". The term macrocyclicasused herein means a cyclic organic compound having a ring containing atleast ten atoms. Comprising essentially" means that the materials andprocess steps specified are essential; however, other materials andprocess steps can be used provided they do not significantly adverselyaffect the invention.

The term arylene" is intended to include phenylene, naphthylene,anthrylene, phenanthrylene, and other polynuclear aromatic moieties;phenylene is preferred.

By derivative of an arylene dioxy group is meant substitutionderivatives of the aromatic nucleus wherein the substituents contain no.active hydrogen atoms and include but are not limited to halo, nitro,azo, alkyl, aryl, aralkyl, alkoxy, cyano groups and the like. Alsoincluded as derivatives of an arylene dioxy group are the saturated ringsystems formed by the hydrogenation of the aromatic nuclei or theirsubstitution products. The crown compounds are described herein bysystematic names. These names are illustrated by the following formulaein which the ring positions are marked.

15 17 Mpg W18 4" 013 10 1'2,5,8,15,18,21-hexaoxatrieyclo[20.4.0.0-]hexacosane compounds can berepresented by the general formula where Q and R can be divalent arylenegroups with bonds attached to vicinal carbon atoms or derivativesthereof and R additionally can be -CH -CH Where R is -CH -CH n +m can bethree to eight inclusive.

Where R is an arylene group or a derivative thereof, It can be from oneto nine and m can be from two to nine.

The above class of compounds can be made with particular ease, as willbecome apparent from a description of the mode of synthesis describedhereinafter.

Another preferred class of crown compounds useful in this inventioncorresponds to the formula o-omcmonp A general procedure for thesynthesis of the crown compounds involves the following reactants:

a. a vicinal dihydroxy aromatic compound such as catechol.

b. an a, w-alkylene diprimary dihalide or aw-alkylene ether diprimarydihalide compound in which the halogen and oxygen atoms are separated bychains of two to six carbon atoms, wherein the halogen is preferablychlorine, but can also be bromine or iodine; and

c. at least one equivalent of a strong base, preferably sodiumhydroxide, for each phenolic hydroxyl group. In general, equimolarquantities of (a) and (b) are consumed. The detailed procedure isselected to favor the particular type of crown compound desired andvaries depending upon the na- L 2N8X 211,0

wherein L is a divalent organic group, which together with X is theether compound of reactant (b) having at least two oxygen atoms andwherein X is halogen. For example in making the preferred compounds,

own on o The compound X-L-X is X(CH,CH,0), CH,CH,X where p is from oneto seven.

7 In some instances, a significant proportion of polyaromatic crowncompound can be formed, e.g. by incorporation of two molecules ofdihydric phenol and two molecules of dihalide. Typical reactions are asfollows:

wherein L is a divalent group which together with X is either ithealltylene or alkylene ether dihalide reactant of (b), or both, andwherein X is halogen. It is to be understood that gmonoaromatic crownproducts of this type given by reaction (I) will be present too.However, it is usually preferable particularly when mired L groups aredesired, to make the polyaromatic crown compound by a sequence ofreactions characterized by the use of partially blocked dihydric phenolsduring the fonnation of at least one of the ring ether groups byreaction of the residual (unblocked) phenolic hydroxyl groups @with areactant (b). Later the blocked hydroxyl groups are regenerated forfurther condensation reactions with the same or different reactant (b).The blocked groupmust be stable toward baae under the conditions of thereaction with X-L-X. Regeneration of the phenolic hydroxyl groupafterward should not adversely affect the ether groups present. It isconvenient to block the phenolic hydroxyl group by reaction with 65dihydropyran, typically.

H NaCl 3,0

The blocked phenol is then reacted with the halide where Z is theblocking unit, e.g.

-Cl-l,-0CH,

Treatment with acid gives a dihydric compound The dihydric compound canbe isolated and purified, if desired. It may be partially blocked or itmay be reacted directly with reactant (b). For example, the dihydriccompound can be treated with a mole of X-L-X, wherein L is the same or adifferent divalent group to give the diaromatic crown compound.

(VII) OL-O + ZNaX H O OL-O By employing a reactant (b) containing anaromatic nucleus, the number of such nuclei appearing in the polyetherproduct can be increased to three or more. Other methods for determiningthe placement and quantity of aromatic nuclei in the final product willbe obvious to the skilled chemist by reference to the foregoingreactions.

it is apparent that the particular dihalide or ether compound chosen forreactant (b) will determine, in part the quantity and composition of thering atoms of the final product, with the hydroxyl oxygens and vicinalcarbon atoms of the arcmatic nucleus making up the remainder of thering. The preparation of the crown compounds used in the presentinvention is not limited to the foregoing typical procedures since othermethods are obviously applicable to obtain the macrocyclic polyethershereinbefore defined.

Generally, the crown compounds are made in a solvent. in order to getgood results, it is desirable that the solvent diasolve the basicreagent 3 well as the dihydric phenol and the dihalide. l lepresentative solvent systems include mixtures of hydroxide or tetraethylammonium hydroxide.

The reaction can be carried out over a wide range of temperatures. Foroperating convenience, temperatures from about 90 to about 140 C. arepreferred. The reaction time will vary depending upon the temperatureand other factors. Other conditions being equal, the higher thetemperature the shorter the time. Typically, time has ranged from about6 hours to about 24 hours. The most suitable time and temperature for aparticular set of reactants can be determined by routineexperimentation.

The crown product can be isolated by conventional methods such as byconcentration of the reaction mixture or by mechanical collection ofinsoluble (or precipitated) product. The crown compounds are freed fromimpurities, such as open-chain polyethers, by recrystallization fromorganic liquids such as alcohol, chloroform, 2-etholy-ethanol, benzeneand heptane.

Saturated cyclic polyether crown compounds having a macrocyclicpolyether ring fused to hydrogenated aromatic rings are preferred inthisinvention. Such compounds can be made by catalytic hydrogenation of thecorresponding aromatic compounds such as those described hereinabove bytechniques familiar to those skilled in the art. Suitable hydrogenationcatalysts are ruthenium dioxide, ruthenium dioxide on charcoal,ruthenium dioxide on alumina, platinum oxide and platinum on charcoal.The solvent can be any suitable hydrogenation solvent which willdissolve the crown compounds. Dioxane is suitable as a solvent. Thearomatic crown complexes of nonreducible salts such as the alkalihalides can be hydrogenated in alcohols such as methanol and n-butanol.

The temperature of hydrogenation is suitably from 60 to 120 C. Pressurescan range from 500 to 2000 p.s.i.g. Typical times required are from 3 to20 hours. It will be realized, however, that these values are notcritical.

Some cleavage of the macrocyclic polyether ring occurs, leading to theformation of dihydric alcohol by products in addition to the desiredhydrogenation product. These products can be separated and the desiredhydrogenation products can be isolated by conventional physical methods,such as fractional crystallization and the like from solvents such asal- I cohol, chloroform, Z-ethoxy ethanol, benzene and heptane, or

the resulting crown complex is soluble in the isocyanate to be bychromatographic separation. if the desired product does not otherwisecontain active hydrogen groups, the reaction product can be reacted withreagents such as organic isocyanates, which react readily with hydroxycompounds, to facilitate separation of the products. Further informationregarding the preparation and properties of the crown compoundsincluding numerous representative species appears in applicant'scopending application Ser. No. 588,302, filed Oct. 2 i 1966, nowabandoned.

The isocyanate trimerization catalysts of this invention are complexesof the crown compounds described above and the cation of a basic alkalimetal salt. Each cation complexes with at least one molecule of thecrown compound. Most complexes have 1:] ratio of cation to crowncompound; however, some of the complexes containing larger cations areknown to have a 1:2 ratio. The cation can be organic or inorganic.Regardless of the ratio, the complexes are prepared in the mannerdacribed hereinafter. These complexes will also hereinafter be referredto as "crown complexes." By "basic" is meant a Lewis base. Any of thecrown compounds described in applicant's copending application describedabove can be used. Any basic alkali metal salt can be employed so longas -protonated anion, e.g. (cyclic ether-KOH) +NH,

trimerized. Representative salts are the hydroxides, alkoxides,phenoxides, acetates, 2-ethyl hexanoates, cyanides and benzoates. Thepreferred complexes are those obtained from the saturated cyclicpolyether crown compounds described above and the strongly basic sodiumand potassium salts such as the hydroxide, acetate, Z-ethylhexanoate,amide and cyanide. Especially preferred are complexes of 2,5,8,15,l8,21-hexaoxa-tricyclo[20.4.0.01hexacosane and the potassium salts of phenols,e.g., 2,4,6-tri-tert-butyl phenol, unsubstituted phenol, o-tert-butylphenol and p-tert-butyl phenol. The preferred complexes induce fasterrates of trimerization with minimal formation of isocyanate dimers.

The complexes of the crown compounds with alkali metals I can beprepared by one or more of the following methods:

Method l0ne mole of polyether and one mole the metal compound aredissolved in a suitable solvent which is later removed by evaporationfrom the resulting complex, usually under vacuum.

Method 2-One mole of polyether and one mole or more of the metalcompound are dissolved in a minimum quantity of hot solvent, theresulting complex being precipitated by cooling and mechanicallyseparated, e.g., by filtration, centrifugation, etc.

Method 3-One mole of polyether is heated with one mole or more of themetal compound in a solvent in which only the latter is readily soluble,the polyether being converted into a crystalline complex without thesystem ever becoming a clear solution. The complex is recovered by.filtration.

Method 4-One mole of polyether is warmed with thorough mixing with onemole of the metal compound. No solvent is used.

Method 5-A benzene solution of cyclic ether potassium hydroxide complexof known concentration is reacted with a (cyclic ether-KNH,+H,0)

(cyclic ether-KOH) HOG-N0:

(cyclic otherK0 N0a) :0

The water formed in the reaction can either be left in the solu havingoxygen atoms disposed therein alternately separated by 7 two and threecarbon atoms, complexes with the alkali metal: are formed only with Liand Na. With macrocyclic polyethers having five oxygen atoms in theringjoined by five chains of two carbon atoms, complexes are formed withLi", Naand K". With macrocyclic compounds having six or more oxygenatoms in the ring joined by six chains of two carbon atoms, complexesare formed with Li, Na*, Kand Cs".

ln complexes of alkali metal compounds, substituents in the macrocyclicpolyether ring do not greatly affect the formation of the crowncomplexes. However, substituents do influence considerably theproperties of the complexes, particularly-the solubility properties ofthe complexes which are formed. In general the saturated crowncompounds, made by the hydrogenation of the aromatic crown compounds,fonn complexes which are more soluble and which are more stable thanFurther details regarding methods of preparation, isolation, solubilitycharacteristics and other properties and representative examples ofcrown complexes useful in this invention can be found in applicant'scopending application Ser. No. 588,302, filed Oct. 21, 1966, nowabandoned.

The basic salt crown complexes are useful for effecting thetrimerization of organic isocyanates in general; including aliphatic,cycloaliphatic, aromatic and aralkyl types having one or more isocyanatogroups per molecule. Representative isocyanates are 4,4'-methylenebis(cyclohexyl 'isocyanate tetramethylene diisocyanate, hexarnethylenediisocyanate, 3- methoxypropyl isocyanate, phenyl isocyanate, ethylisocyanate, 4 -chlorophenyl isocyanate, benzyl isocyanate, xylyleledlbocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,2,4,6-triisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane,naphthalene-1,5-diisocyanate and polymeric polyisocyanates such as thoseprepared by the phosgenation of polyamines present in crude undistilled4,4- methylene dianiline made by condensing aniline and formaldehyde inthe presence of mineral acid. Mixtures of isocyanates can also betrimerized.

The process of this invention is also useful in trimerizing crude orundistilled isocyanate mixtures that contain complex, high molecularweight, tarry materials produced by the reaction of phosgene and anorganic amine. Such phosgenation byproducts are generally considered bythose skilled in the art to be comprised largely of biuret and polymericbiuret molecules having free isocyanato groups. These isocyanato groupscan participate in trimer formation along with the isocyanato groups ofother monoand polyisocyanates present. Successful trimerization of suchcrude isocyanate mixtures is of considerable importance since certaintrimerized crude isocyanate mixtures are especially valuable in thepreparation of polyurethane rigid foams.

The crown complexes of this invention can also be used to cross-linklow-molecular weight polymers having -NCO groups.

The trimerization reaction of this invention can be carried out in thepresence of dry, inert (to the crown complexes and isocyanates) solventssuch as benzene, toluene, acetone and various fluorocarbons such aschlorodifluoromethane. it is possible to prepare solutions of isocyanatetrimers which can be used directly without isolation of the products.Such solutions are especially useful in the formulation of protectivecoatings, impregnating resins, and the like. When the isocyanate to betrimerized is a liquid, no solvent is required. In such cases the solidcrown complex is added directly to the liquid isocyanate.

in carrying out the process of this invention about 0.0 l-l .0 parts ofthe crown complex are employed per 100 parts of isocyanate. Thepreferred quantity of catalyst is about 0.02-0.5 part per I00 parts ofisocyanate. With aromatic isocyanates trimerization can be initiated atroom temperature by merely adding the crown complex to the isocyanate.Due to the exothermic nature of the reaction, the temperature rises ifcooling is not provided. In the case of aliphatic isocyanates whichtrimerize sluggishly relative to aromatic isocyanates, it may bedesirable to heat the reaction mass to provide a reasonable rate ofreaction. In general, the reaction should be carried out as rapidly aspossible and at the lowest temperature practicable. Thebest temperaturerange must be determined for each 'isocyanate since they have varyingdegrees of reactivity, but

can routinely be determined by one skilled in the art.

A preferred procedure for preparing trimers from 2,4- or 2,6-tolue nediisocyanate or mixtures thereof involves adding about 0.03 parts of thecomplex of 2,5, 8,15,18,2l-hexaoxa tricyclol20.4.0.0'-"]hexacosane andthe potassium salt of 2,4,oftri tert-butyl phenol to 100 parts ofdiisocyanate at about 25'-50 C. The complex is conveniently handled inthe form of a concentrated solution in benzene. Following catalystaddition, the reaction mass is allowed to heat up of its own accord. Onreaching a temperature of about l20-l60 C., the reaction stopsautomatically with commercial grades of diisocyanate apparently due todeactivation of the catalyst. When run on a large scale, enough of ahydrolyzable chlorine compound such as benzoyl chloride should bepresent in the diisocyanate prior to catalyst addition to provide about0.2 percent by weight hydrolyzable chlorine. This insures cut off of thereaction at l20-l60 C. At this point, about 40-60percent of the toluenediisocyanate has been converted to trimer and 7 very little polymericmaterial has been formed. The solution of trimer in diisocyanate can beused as such, diluted with additional diisocyanate, or isolated byremoving unreacted diisocyanate by vacuum distillation.

The catalysts of this invention have many advantages over those of theprior art. They are safe to handle, can be used in relativelylow-concentrations and when used as directed above, do not cause theformation of significant amounts of the dimer or polymerization beyondthe trimer stage.

The invention will now be illustrated by reference to the followingexamples wherein parts and percentages are by weight unless otherwiseindicated. Throughout the examples, the following abbreviations areused.

Crown XXXlX" 2,5,8, 1 5, l 8,2 l -h exaoxa-tricyclo-[20.4.0.0-"]hexacosane. 28 alcohol" a denatured alcohol compositionconsisting of 9l.75 percent by weight ethyl alcohol, 0.5 percent byweight benzene and the remainder water.

Crown XVIII" 2,3,] l, l Z-dibenzo-l ,4,7, l 0,1 3, l6-hexoxacyclooctadeca-2, l l-diene.

The invention is further illustrated by the following examples whereinparts and percentages are by weight unless otherwise indicated.

EXAMPLE I One-tenth milliliter of an 0.156 N benzene solution of theCrown XXXIX complex of potassium hydroxide (prepared by method] aboveusing methanol as the solvent) is added to a solution of 2 ml. of phenylisocyanate in 4 ml. of benzene. The temperature of the mixture rises to33 C. within a few minutes. A water bath is used to cool the mixture.After one hour at 25-33 C., precipitated triphenyl isocyanurate isfiltered ofi', washed with hexane to remove solvent and any unreactedphenyl isocyanate, and dried in a vacuum oven at 100' C. The productconsists of 1.88 g. of white solid, m.p. 275-28 0 C. The melting pointof triphenyl isocyanurate is known to be 280C, (Jones and Savill, J.Chem. Soc., 4392 (1957)).

EXAMPLE 2 Two milliliters of phenyl isocyanate, 3 ml. of benzene, and 3drops of Crown XXXlX -NH, complex in benzene (0.25 percent nitrogen,made by method 5 above) are mixed in a 20 ml. vial at 26 C. After 33minutes copious amounts of white solids have formed. The mixture istriturated with 20 ml. of n-heptane and dried in a vacuum oven at 40 C.The product consists of 2.08 g. (95.4 percent yield) of crystallinesolid, m.p. 277-278 C.

EXAMPLE 3 To a solution of 5 ml. of ethyl isocyanate in 40 ml. ofbenzene is added 0.2 ml. of 0.156 N Crown XXXIX-KOH complex in benzene(prepared by method 1 above using methanol as the solvent). The mixtureis refluxed in an atmosphere of nitrogen for two hours, after which thevolatile constituents are evaporated under reduced pressure to leave 2.6g. of an oily solid. This is recrystallized from 28 alcohol to give 1.91g. of triethyl isocyanurate, m.p. 87-90 C. The melting point of triethylisocyanurate is known to be C. (Ber. 3, 765 (I870).

EXAMPLE 4 Forty milliliters of 2,4-toluene diisocyanate is stirred andheated to 50 C. in an atmosphere of nitrogen, and 0.2 ml. of an 0.l5 Msolution of the complex of Crown XXXlX and potassium 2,4,6-tri-t-butylphenolate in benzene (made by The reaction is slowly heated to 220 C.over a five-hour period at 0.2-0.5 tor., during which time 22 ml. ofdistillate, primarily unchanged toluene diisocyanate, is collected. Theresidue is a yellow, benzene-soluble resin containing 22.1 percent freeNCO groups. Pure toluene diisocyanate trimer would contain 24.1 percent-NCO groups. lnfrared spectral analysis confirms the presence of thetrimer (isocyanurate structure).

EXAMPLE An electrically heated stirred resin kettle is charged with 200ml. of 80:20 mixture of 2,4- and 2,6-toluene diisocyanate and 2.2 ml. ofan 0.1 M solution of Crown XXXlX and potassium 2,4,6-tri-t-butylphenolate complex in toluene made by method 5 above except the solventis toluene. The mixture heats to 150 C. in 6 minutes and is thenevacuated with a mechanical pump. Unchanged toluene diisocyanatedistills out. After 24 minutes a final temperature of 162 C. is reached,and the mixture is too viscous to stir. The mixture is heated to 200 C.and vacuum maintained for an additional 0.5 hour. After cooling undernitrogen, the remaining resinous is found to contain 21.9 percent freeNCO groups. lnfrared spectral studies of the product shown the presenceof the trimer.

EXAMPLE 6 Thirty-five milliliters of a 0.0175 N solution of Crown XVIIIand potassium hydroxide complex (made in methanol by method 1 above) indimethyl sulfoxide is added dropwise to 200 ml. of 80:20 2,4-, 2,6 TDlwhile stirring. The temperature of the mixture rises to 35 C. duringthis period. The reaction continues exothermically, and after 6 minutesof additional stirring the mixture has reached a temperature of 107 C.The kettle is evacuated with a mechanical pump, and unreacted TB] isallowed to distill out. The trimerized residue consists of 200 grams ofa brittle resin containing 20.0 percent free-NCO groups. The trimer isidentified by infrared analysis.

All of the products prepared in the foregoing examples contain less than1 percent by weight isocyanate dimers.

What is claimed is:

1. A process for trimerizing organic isocyanates which consistsessentially of mixing said isocyanates with a catalytic quantity of acomplex of a basic alkali metal salt and one to two moles per gram-atomof the cation of said salt of a macrocyclic polyether consisting of oneor two arylene dioxy groups or derivatives thereof,

said arylene dioxy groups being phenylene,

naphthylene, anthrylene, or phenanthrylene dioxy groups, and saidderivatives of arylene dioxy groups being a. substituted derivatives ofsaid arylene dioxy groups wherein the substituents are halo,

nitro, azo, alkyl,

aryl, aralkyl, alkoxy or cyano,

b. fully saturated hydrogenated products of said arylene dioxy groups,or

c. fully saturated hydrogenated products of the substituted arylenedioxy groups enumerated in (a) above, joined together to form amacrocyclic polyether ring of 14-60 atoms by a, w-diprimary C -Calkylene or am-diprimary C -C alkylene ether groups, the oxygen atoms ofsaid macrocyclic ring being separated by two or three carbon atoms.

2. A process of claim 1 wherein the macrocyclic polyether has theformula wherein Q is a vicinal phenylene group or the fully hydrogenatedderivative thereof and R is the same as Q or an ethylene group.

3. A process of claim 2 wherein the basic alkali metal salt is a sodiumor potassium hydroxide, amide, acetate, 2-ethyl hexanoate, cyanide orphenolate.

4. A process of claim 2 wherein the basic alkali metal salt is apotassium phenolate.

5. A process of claim 2 wherein the macrocyclic polyether has theformula 0 01520111 0 n \0(CH2CH3O m wherein n is from one to nine and mis from two to nine.

6. A process of claim 5 wherein the basic alkali metal salt is a sodiumor potassium hydroxide, amide, acetate, 2-ethyl hexanoate, cyanide orphenolate.

7. A process of claim 2 wherein the said macrocyclic polyether has theformula wherein n +m is from three to eight.

8. A process of claim 7 wherein the basic alkali metal salt is a sodiumor potassium hydroxide, amide, acetate, 2-ethyl hexanoate, cyanide orphenolate.

9. A process of claim 2 wherein said has the formula 0(CHgCHgO n OO(CH1CH,O m

wherein n is from one to nine and m is from two to nine.

10. A process of claim 9 wherein the alkali metal salt is a sodium orpotassium hydroxide, amide, acetate, 2-ethyl hexanoate, cyanide orphenolate.

11. A process of claim 9 wherein the basic alkali metal is a potassiumphenolate.

12. A process of claim 9 wherein the macrocyclic polyether is2,3,11,12,-dibenzo-l,4,7,l0,I3,l6-hexoxacyclo-octadeca- 2,11-diene andthe basic alkali metal salt is sodium or potassium hydroxide, amide,acetate, 2-ethyl hexanoate, cyanide or phenolate.

13. A process of claim 12 wherein the organic isocyanate is a tolylenediisocyanate.

[4. A process of claim 2 wherein the macrocyclic polyether has theformula macrocyclic polyether (EH2 CH2 wherein n +m is from 3 to 8.

15. A process of claim 14 wherein the basic alkali metal salt is asodium or potassium hydroxide, amide, acetate, 2-ethyl hexanoate,cyanide or phenolate.

16. A process of claim 15 wherein the isocyanate is a tolylenediisocyanate.

* k i i 0

2. A process of claim 1 wherein the macrocyclic polyether has theformula
 3. A process of claim 2 wherein the basic alkali metal salt is asodium or potassium hydroxide, amide, acetate, 2-ethyl hexanoate,cyanide or phenolate.
 4. A process of claim 2 wherein the basic alkalimetal salt is a potassium phenolate.
 5. A process of claim 2 wherein themacrocyclic polyether has the formula
 6. A process of claim 5 whereinthe basic alkali metal salt is a sodium or potassium hydroxide, amide,acetate, 2-ethyl hexanoate, cyanide or phenolate.
 7. A process of claim2 wherein the said macrocyclic polyether has the formula
 8. A process ofclaim 7 wherein the basic alkali metal salt is a sodium or potassiumhydroxide, amide, acetate, 2-ethyl hexanoate, cyanide or phenolate.
 9. Aprocess of claim 2 wherein said macrocyclic polyether has the formula10. A process of claim 9 wherein the alkali metal salt is a sodium orpotassium hydroxide, amide, acetate, 2-ethyl hexanoate, cyanide orphenolaTe.
 11. A process of claim 9 wherein the basic alkali metal is apotassium phenolate.
 12. A process of claim 9 wherein the macrocyclicpolyether is 2,3,11,12-dibenzo-1,4,7,10,13,16-hexoxacyclooctadeca-2,11-diene and thebasic alkali metal salt is sodium or potassium hydroxide, amide,acetate, 2-ethyl hexanoate, cyanide or phenolate.
 13. A process of claim12 wherein the organic isocyanate is a tolylene diisocyanate.
 14. Aprocess of claim 2 wherein the macrocyclic polyether has the formula 15.A process of claim 14 wherein the basic alkali metal salt is a sodium orpotassium hydroxide, amide, acetate, 2-ethyl hexanoate, cyanide orphenolate.
 16. A process of claim 15 wherein the isocyanate is atolylene diisocyanate.